Azo dyestuffs and process of producing the same



Patented Apr. 1930 UNITED STATES PATENT OFFICE O'I'I'O BOHST, OE HOCEST-ON-THE-IAIN, GERMANY, ASSIGNOR '10 GENERAL ANILINE WORKB, INC., 01' NEW YORK, N. Y., A CQBPOR ATION OF DELAWARE AZO DYEST'UITB AND PROCESS OF PRODUCING THE SAME Io Drawing, Application fled lune 28, 19b6, Serial No. 118,850, and in Germany July 7, 1925.

My present invention relates to new azo dyestuifs and a process of preparing them.

I have found that dyestuffs, possessing excellent properties as to fastness, are obtained 5 by combining diazotized arylsulfonic acid-oaminoaryl-alkyl (or aralkyl) amides of the general formula:

i-som-nkyl-emik n aryl-ortho-NH:

ar l-) ortho-nitro-aryl amines and subsequent y reducing the resulting products or by alkylating and reducing the'ortho-nitro derivatives obtainable by the method described as in German Patent No. 164,130, or they may be produced according to the statements contained in U. S. Patent No. 1,540,164, by the action of arylsulfo-"chlorides upon orthonitranilines or monoacet-yl-o-phenlyene-dio amine, alkylation and subsequent reduction .or splitting off of the acet 1 group.

Among the sulfo-chlori es there may be used in my new process for instance benzenesulfo-chloride, -toluenesulfo-chloride,chlorbenzenesulfoch oride, dichlorbenzenesulfochloride or the like; among the o-nitro-arylamines and monoacetyl-o-diamines for instance: o-nitraniline, m-nitro-p-toluidine, onitro-p-alkylhydroxy aniline, o-nitro-p-chloraniline, monoacetyl-o-phenylenediamine,

monoacetyl-o-toluylenediamine, monoacetylo-diaminophenetol or the like.

The followingexamples serve to illustrate my invention but are not intended to limit it thereto, the parts being by weight:

1. 5,2 parts of benzenesulfonic acid-o.- aminophenyl-methylamide arerubbed with 50 parts of water and 7 parts of hydrochloric acid of B.; the mixture is cooled with ice and then diazotized in the usual manner with a solution of 1,4 parts of sodium nitrite. The diazo compound first separates as a resinous mass, but solidifies after some time and can then be triturated. The paste thus obtained is introduced, while stirring, into a solution of 6,2 parts of 2.3-oxynaphthoic acid-2'-methyl-1-anilide in 300 parts of water and 10 parts of caustic soda solution of 40 B.

Thus, a scarlet-red precipitate is immediately formed which can be filtered and dried. The dyestufi has most probably the formula:

OH 1 CH -If equivalent quantities of the diazo compounds of other arylsulfo-o-amino-alkylarylamides are used and combined with equivalent quantities of other 2.3-oxynaphthoio acid arylamides, similar red precipitates are obtained.

2. For producing a red dyeing there is used a bottoming bath prepared with:

13.2 grams of 2.3-oxynaphthoic acid-4'- chlor-2'-methyl- 1'-anilide, 30 cc. of caustic soda solution of 34 B., 30 cc. of sodium Turkey-red oil 50% strength, 500 cc. of boiling water, made up with cold water to one litre.

The material is impregnated and developed in a diazotizing bath prepared as follows: 5.2 grams of benzene sulfonic acid-o-aminophenyl-methylamide are diazotized as indicated in Example 1. The liquor is made up to one liter and before being used is neutralized with 5 grams of sodium acetate.

When the developing operation is completed,

wherein X stands for hy'cl'afogen or atomic grouping v on ex-o1 i3 1;

The dyestufl has most probably the following formula:

and R for en aryl group the hydrogen atoms of which may be substituted. N+ Hs 2. Process COBSISUH; 3D causlng the (112120 compoune of n base of general formula: f :LyI-SOg-N-ilnlbrtho-NH:

wherein 1 stands 'an alkyl or aralkyl '2' 2' eo m1 1 Cl group. and wherein .l ydrogen Moms of 0 a 1 I the aryl groups ma; oe substituted, co act upon an e015. amide oi be following composition:

\Vhen using for the preparation of the bottoming bath equivalent quantities 01% 0th? n 4 2.3-oxynaphthoic acid ylamides and dev A. \r f see oping with equivalent quantifies of the diam I w compounds of other ai'ylsulfonie acid-o V aminoaryl-alkyl (or arelkyl) amides, there are also obtained dyeings of excellent lash ness, the shades of which generally vary from brown-red to yellowish-red to bluish-red.

3. Process consisting; in causing the diazo compound of a base of for-mule:

NHI

The following table shows the properties h of a number of dyestufis obtalnable by my Osorm new process: 3H:

Diazotizing base Coupling com ponents Shade N0. 1 1-to1uenesulfone-benzylamino-Z-am1no-4-methy1benzene 'figfiggg Red No. 2 1-toluenesulfone'benzylemloo-2nmino'-methylbenzene QJl-OXynnphthoiC acidm naphthylumide Red No. 3 Ltoluenesulfone-beuzylam1no-2-nmino-4-methylbenzene 2. xynaphthoic a cid-l lphthylumide Red No. 4 l-benzeuesulfone-methylnmino-iZ-qminc-benzene igfiggg Red No. 5 l'benzenesulfone-methylumino-iZ-umlnwbenzene 2.8-oxynaphthoic acid-a-naphthylamide Red No. 6 l-bemenesultone-methylamlno'fl-nmmo-benzene 2.3oxynaphthoic g cid-d-nnnhthylamiqe Red No. 7 l-ben1eneaul{one-methylumino-il-umino--chlorobenzene igggg s Red No. 8 l-benzenesulfone-methylamin0-2 amino-4-ch1orobenzene 2.3-oxprnnphtholc ncid-w-naphthylamide Red No. 9 l-benzeneaul{one-methylamino-2-arnne4-chlorobenzene 2.3-oxynuphthoic acid-,J-nuphthylamide Red No.10 1-benzeneaulfone-methylamin0-2-am1no-4-ethoxy ben- 2.3-oxy.uuphth0ic-5-chloro-2-methyl-1- Bed zeue anilide m No. 11 1 blegzeeneaultone methylamino2 am.no .4 ethoxy ben zrgpxynaphthoic acimpmaputhylamide Red No.12 Llfianlienesulfone-methylam1no-2-nmino-n-etnoxy benzsmxynaphmoic acmfimflphthylamide muishmed f 'gz 2.3-oxynaphthoic aciG-Bwmphthylemifie Bluish-red No. 14 2-benlenesul(one-methylamino-l-amino-napthalene 2.3-ozzynaphfl1oic acid qhmphthylamide Claret-red Iclaim: to act upon en acid amide of the following 1. Process consistin in causing the diezo compound of a base 0 the general i'formul;

lryl-BOrN-cryl-ortho-NH:

O i. products, compounds of she following formula:

uwl-fiM-N-ml (crtho)-2 1 wherein R stands for an alkyl g up, and wherein the hydrogen stems C the aryl groups may be substi euted, to em, ,3 1., upon an acid amide of the following COmPOSl" A tion: g'" @013 rmoo-nn mz on w 0N-B:.X "wherein R hands for en a 1 or eralkyl 1 group, "rogen atoms of t e eryl group may be substituted, and X stands for hydrogen or the atomic grouping:

aryl-BOz-N-sryl (oi-tho) wherein the hydrogen atoms of the aryl groups may besubstituted and R stands for an alkyl or aralkyl group, said compounds being dyestuffs of varied red tints, insoluble inwater, recrystallizable from glacial acetic acid, and soluble in concentrated sulfuric acid to a red solution.

5. As new products, compounds of the following formula sryl-BOa-N-aryl (than Q I 0H CH:

the said compound being a bright red dyestufl, insoluble in water, crystallizable from glacial acetic acid in the form of red needles and soluble in concentrated sulfuric acid to a red solution. I

In testimony whereof, I aifix my signature.

' OTTO SOHST. 

